The well-defined structure and high stability of peptides make them attractive biotemplates for low-temperature synthesis of semiconductor nanocrystals. Adsorbed peptide monolayers could also potentially passivate semiconductors by preventing regrowth of the oxide layer. In this work, the adsorption and passivation capabilities of different collagen-binding peptides on InAs surfaces were analyzed by X-ray photoelectron spectroscopy (XPS). Before peptide functionalization, Br(2)- and HCl-based etches were used to remove the native oxide layer on the InAs surfaces. The presence of the N 1s peak for peptide-functionalized samples confirms the adsorption of peptides onto the etched InAs surfaces. Calculated coverages were similar for all peptide sequences and ranged from ∼20 to 40% of a monolayer using the deconvoluted C 1s spectra and from ∼2 to 5% for the N 1s spectra. The passivation ability of the peptides was analyzed by comparing the ratios of the oxide components to the nonoxide components in the XPS spectra. The thickness of the oxide layer was also approximated by accounting for the attenuation of the substrate photoelectrons through the oxide layer. We find that the oxide layer regrowth still occurs after peptide functionalization. However, the oxide layer thicknesses for peptide-functionalized samples do not reach as received levels, indicating that the peptides do have some passivation ability on InAs.
In a variety of applications where the electronic and optical characteristics of traditional, siliconbased materials are inadequate, recently researchers have employed semiconductors made from combinations of group III and V elements such as InAs. InAs has a narrow band gap and very high electron mobility in the near-surface region, which makes it an attractive material for high performance transistors, optical applications, and chemical sensing. However, silicon-based materials remain the top semiconductors of choice for biological applications, in part because of their relatively low toxicity. In contrast to silicon, InAs forms an unstable oxide layer under ambient conditions, which can corrode over time and leach toxic indium and arsenic components. To make InAs more attractive for biological applications, researchers have investigated passivation, chemical and electronic stabilization, of the surface by adlayer adsorption. Because of the simplicity, low cost, and flexibility in the type of passivating molecule used, many researchers are currently exploring wet-chemical methods of passivation. This Account summarizes much of the recent work on the chemical passivation of InAs with a particular focus on the chemical stability of the surface and prevention of oxide regrowth. We review the various methods of surface preparation and discuss how crystal orientation affects the chemical properties of the surface. The correct etching of InAs is critical as researchers prepare the surface for subsequent adlayer adsorption. HCl etchants combined with a postetch annealing step allow the tuning of the chemical properties in the near-surface region to either arsenic- or indium-rich environments. Bromine etchants create indium-rich surfaces and do not require annealing after etching; however, bromine etchants are harsh and potentially destructive to the surface. The simultaneous use of NH(4)OH etchants with passivating molecules prevents contact with ambient air that can occur during sample transfer between solutions. The passivation of InAs is dominated by sulfur-based molecules, which form stable In-S bonds on the InAs surface. Both sulfides and alkanethiols form well-defined monolayers on InAs and are dominated by In-S interactions. Sulfur-passivated InAs surfaces prevent regrowth of the surface oxide layer and are more stable in air than unpassivated surfaces. Although functionalization of InAs with sulfur-based molecules effectively passivates the surface, future sensing applications may require the adsorption of functional biomolecules onto the InAs surface. Current research in this area focuses on the passivation abilities of biomolecules such as collagen binding peptides and amino acids. These biomolecules can physically adsorb onto InAs, and they demonstrate some passivation ability but not to the extent of sulfur-based molecules. Because these adsorbents do not form covalent bonds with the InAs surface, they do not effectively block oxide regrowth. A mixed adlayer containing a biomolecule and a thiol on the InA...
The band gap of indium gallium nitride can be tuned by varying the compositional ratio of indium to gallium, spanning the entire visible region and extending into the near-infrared and near-ultraviolet. This tunability allows for device optimization specific to different applications, including as a biosensor or platform for studying biological interactions. However, these rely on chemically dependent interactions between the device surface and the biostructures of interest. This study presents a material gradient of changing In:Ga composition and the subsequent evaluation of amino acid adsorption to this surface. Arginine is adsorbed to the surface in conditions both above and below the isoelectric point, providing insight to the role of electrostatic interactions in interface formation. These electrostatics are the driving force of the observed adsorption behaviors, with protonated amino acid demonstrating increased adsorption as a function of native surface oxide buildup. We thus present a gradient inorganic substrate featuring varying affinity for amino acid adhesion, which can be applied in generating gradient architectures for biosensors and studying cellular behaviors without application of specialized patterning processes.
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